Method for the production of sulphur-containing terpene compounds



Patented Mar. 17, 1936 UNITED STATES METHOD FOR THE PRODUCTION OF SUL-PHUR-CONTAINING TERPENE COM- POUNDS Emil Ott, Elsmere, Del., assignor toHercules Powder Company, Wi ration of Delaware N Drawing. Appli SerialNo.

17 Claims. This invention relates to the production of particularly tothe production of such products from halogenated terpene compounds.

In application Serial No. 713,304, filed February 28, 1934, by mejointly with Joseph N. Borglin,

By such methods, however, it is not possible to producesulphur-conmetal, the ammonium group is 1 or more.

or substitution products of terpene compounds are all well known and areusually prepared by direct treatment of the de-' sired terpene compoundwith the halogenor with a hydrogen halide. Chlorine and bromine are thehalogens usually employed. They may also be produced by the use ofsulphur halides, acid halides, etc.

Any compound containing the group -SnM, as above defined, may beemployed in the method in accordance with this invention, as, forexample. hydrogen sulphide; metal hydrosulphides, as sodium, potassiumhydrosulphides, etc. phides, as sodium potassium, calcium, bariumsulphides, etc.; metal polysulphides, a sodium polysulphide, metalthiocyanates, etc. organic compounds containing the -SH group, as, forexample, mercaptans, as ethyl, benzyl, pinene mercaptans, thiophenol,mercapto-abietic acid, etc.; thioacids; xanthates; trithiocarbonates;etc.; organic compounds containing the -SM group, where M is a orhydrogen, and n 'I-Ialogen addition The halogenated terpene compound andthe sulphur compound of the type described may be reacted in anyproportion, depending on the molecular composition of the productstobereacted lmington, DeL, a corpocation June '1, 1935,

and the product desired, and also on the relative cost of reagents,altho where optimum reaction rates and yields are desired, a ratio offrom about 1 part to about parts by weight of sulphur compound per partof halogenated terpene compound is to be preferred. The reaction willpreferably be carried out at an elevated temperature in order to securea practical reaction rate, however, the reaction occurs at a temperatureof from about 0 C. up to the decomposition temperature of the reactants.A temperature of from about 60 C. to about 110 C. is very satisfactory.Pres-- sure conditions have slight effect upon the reaction, exceptwhere hydrogen sulphide is employed, in which case super-atmosphericpressure may be employed to advantage. r i

The sulphur compound, ifsolid, will preferably be dissolved in anorganic solvent therefor, as for example; ethyl alcohol, methyl alcohol,acetone, etc., or even in water, or in mixtures of such solvents,depending on its solubility. The halogenated terpene compounds, ifliquids, will ordinarily be used in such form in the -reaction,- and thesolvent selected for the sulphur compound will preferably be misciblewith the halogenated terpene compound. If the halogented terpenecompound is solid, it will desirably be dissolved, either in the samesolvent as that used for the sulphur compound or in a solvent misciblewith such employed is hydrogen sulfide, the hydrogen sulphide willdesirably be bubbled through the halogenated terpene compound, which ifnot a liquid, will be in solution.

After the completion of the reaction, which will usually take from aboutA, to about hours, depending upon the particular conditions of re actionemployed, the sulphur-containing terpene compound may be recovered fromthe reaction mixture, for example, by extracting the latter, preferablyafter acidification, with a solvent for the reaction product which is anon-solvent for the unreacted sulphur compound and the like impurities,as, for example, with carbon tetrachloride, benzene, gasoline, etc., orby a variety of other methods, obvious to those skilled in the art,depending on the chemical and physical nature of the particular reactionmixture. A preliminary extraction of the non-acidified reaction mixturewill remove most of the unreacted halogenated terpene compound, togetherwith some partially suitable procedure, as distillation, preferably invacuo, extraction, etc:

solvent. When the sulphur compound a Diverse types of sulphur-containingterpene compounds may be produced in accordance with this invention.Thus, for example, and depending upon the type of sulphur compound.employed, terpene mercaptans or thioalcohols; terpene sulphides orthioethers; mixed terpene and alkyl, aryl or aralkyl thioethers; terpenedior polysulphides; terpene thioacids or derivatives thereof; etc.; maybe formed.

If desired, the halogenated terpene compound may be admixed with otherorganic halogencompounds, and the resultant mixture treated with asulphur compound of the type described in accordance with thisinvention.

When hydrogen sulphide is to be used as the sulphur compound inaccordance with this invention, it is not necessary to first halogenatea terpene compound and then react the halogenated compound with thehydrogen sulphide. If desired, the two reactions may proceedsimultaneously. Thus, a terpene compound may be treated in accordancewith this invention simultaneously with a halogen and with hydrogensulphide.

The following examples are illustrative of practical procedure inaccordance with this invention:

Example I The once extracted aqueous layer was acidified with aceticacid and again extracted with carbon tetrachloride. The extract was thenwater washed and evaporated. The product analyzed: Clz 1.4% S 40%Example II An excess of potassium hydrosulphide in alcohol was added tochlorinated alpha-terpinene which contained 31% C12. These reactantswere 'refiuxed two hours, cooled and water washed. The resulting oilgave a positive doctor test for mercaptan and-analyzed:

S 5.5% C12 13.4% Example III Chlorinated pinene was refluxed eight hoursTo 20 g. of chlorinated pinene (23% C12) was added 20 cc. of aqueousNHlSl-l solution containing 7.0 g. of NH4SI-I. To this was added cc. ofalcohol and 25 cc. of benzene. This mixture was refluxed for about 3hours. It was then washed with water until free of the ammoniumhydrosulphide solution. The reaction mixture was then freed of water andthe product recovered by the evaporation of benzene. The product gave apositive mercaptan test and analyzed 4.7% sulphur.

Example V gen sulphide remained as shown by test. The final product gavea positive test for mercaptan and analyzed 0.44% sulphur.

Example VI 50 cc. of alcoholic potassium pinene mercaptide was preparedby reacting 15 cc. of caustic extracted pinene mercaptan (14% S) withthe theoretical amount of KOH in alcohol. To this was added 4 g. ofchlorinated pinene (23% C12) and the mixture warmed on the steam bathfor about two hours. A white precipitate of KCl was filtered out and thereaction mixture then washed with alcohol. Most of the alcohol was thenevaporated from the reaction mass, which was then dissolved in ether.This solution was then washed several times with dilute causticto removeany mercaptan. The reaction product was then recovered in the form of aviscous oil which analyzed 11.70% sulphur.

Example VII 10 cc. of chlorinated pinene (23% C12), 10 cc. of ethylmercaptan and 2 g. of anhydrous aluminum chloride were well mixed andallowed to stand for two hours. The reaction mass was washed with waterdilute hydrochloric acid and then with water. It was then freed of waterby a drying agent and the ethyl mercaptan removed by evaporation. Thereaction product gave a negative test for mercaptan, but a positive testfor sulphur.

It will be understood that the details and examples hereinbefore setforth are illustrative only, and do not in any way limit the inventionas herein broadly described and claimed.

What I claim and desire to protect by Letters Patent is:

l. The method of producing a sulphur-containing terpene product whichincludes reacting a halogenated terpene compound with acompoundcontaining the group -SnM, where M is a metal, the ammonium-group orhydrogen and n is l or more.

2. The method of producing a sulphur-containing terpene product whichincludes reacting ahalogenated terpene compound with a compoundcontaining the group 'SnM, where M is a metal and n is 1 or more.

3. The method of producing a sulphur-containing terpene product whichincludes reacting a halogenated terpene compound with an inorganiccompound containing the group '-SnM, where M is a metal, the ammoniumgroup or hydrogen and n is 1 or more.

4. The method of producingasulphur-containing terpene product whichincludes reacting a halogenated terpene compound with an organiccompound containing the group -SnM, where M is a metal, the ammoniumgroup or hydrogen and n isl or more.

5. The method of producing a sulphur-containing terpene product whichincludes reacting a halogenated terpene compound with hydrogen sulfide.

6. The method of producing a sulphur-containing terpene product whichincludes reacting at a temperature of from about 60 C. to about 110 C. ahalogenated terpene compound with a compound containing the group -SnM,where M is a metal, the ammonium group or hydrogen and n is 1 or more.

pound containing the group -SnM, where M is a metal, the ammonium groupor hydrogen and n is 1 or more.

containing the group -SnM, where M is a metal, the ammonium group orhydrogen and n is 1 or more.

a halogenated terpene ketone with a compound containing the group SnM,where M is a metal, the ammonium group or hydrogen and n is 1 or more.

10. The method of producing a sulphur-containing terpene product whichincludes simultaneously reacting a terpene compound with a halogen andhydrogen sulphide.

11. The method of producing a sulphur-containing terpene product whichincludes reacting a halogenated terpene compound with a compoundcontaining the group -SnM, where M is a metal, the ammonium group orhydrogen and n is 1 or more, and separating the sulphur-containingterpene product from the reaction mixture.

12. The method of producing a sulphur-containing terpene product withincludes reacting a halogenated terpene compound with a compoundcontaining the group -SnM, where M is a metal, the ammonium group orhydrogen and n is 1 or more, and extracting the sulphur-containingterpene product from the reaction mixture with a solvent therefor.

13. The method of producing a sulphur-containing terpene product whichincludes reacting a halogenated terpene compound with an inorganicsulphide.

14. The method of producing a sulphur-containing terpene product whichincludes reacting a halogenated terpene compound with an alkali metalmono-sulphide.

15. The method of producing a. sulphur-containing terpene product whichincludes reacting a halogenated terpene compound with sodium sulphide.

16. The method of producing a sulphur-containing terpene product whichincludes reacting a halogenated terpene compound with a metalthiocyanate.

17. The method of producing a sulphur-containing terpene product whichincludes reacting a halogenated terpene compound with sodiumthiocyanate.

